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Glass transition temperature determination of solid rocket propellants using

various thermal analysis techniques

Conference Paper  in  AIP Conference Proceedings · July 2018

DOI: 10.1063/1.5047603

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Marcin Cegla J. Zmywaczyk

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 Glass Transition Temperature Determination of Solid
Rocket Propellants Using Various Thermal Analysis
Techniques
Marcin Cegła1, a), Janusz Zmywaczyk2, b), Piotr Koniorczyk2, c)
1
Military Institute of Armament Technology, 7 Wyszyńskiego St., 05-220 Zielonka, Poland
2
Faculty of Mechatronics and Aerospace, Military University of Technology, 2 Witolda Urbanowicza Ur St., 00-908
Warsaw, Poland
a)
Corresponding author: ceglam@witu.mil.pl
b)
janusz.zmywaczyk@wat.edu.pl
c)
pkoniorczyk@wat.edu.pl

Abstract. The paper presents results of experimental research of homogeneous and heterogeneous solid rocket
propellants with special attention given to the determination of glass transition temperature. The homogeneous propellant
PAC with density 1.58 g/cm3 and heterogeneous propellant H2 with density 1.77 g/cm3 were subjected to complex
thermo-mechanical analysis with the use of DSC, DIL and DMA techniques. All experiments were conducted with the
use of NETZSCH thermal analysers. Liquid nitrogen was used in order to achieve sub-zero temperature range in which
the glass transition in solid rocket propellants occurs. Differential Scanning Calorimetry experiment was conducted with
the use of DSC 404 F1 Pegasus with the heating rate of 10 K/min in the temperature range from -100 oC to 100 oC The
glass transition of the propellants was determined on the basis of the specific heat change. Thermal expansion was
measured with the use of DIL 402SU dilatometer in the temperature range from -100 oC to110 oC. with the heating rates
of 2 and 10 K/min. Dynamic mechanical analysis conducted in dual cantilever bending mode using the NETZSCH DMA
242C over temperature range from -110 oC to +120 oC, with the heating rate of 2 K/min and the frequency of 1 Hz. The
glass transition was determined for both propellants from the peak of loss modulus curve. The results of conducted
experiments for PAC and H2 solid rocket propellants can be useful in determining the temperature range of safe use and
operation.

INTRODUCTION

Solid rocket propellants are a group of high energy materials containing flammable and oxidizing substances,
enabling them to be combusted in the anaerobic atmosphere. Considering chemical content and the connection
between ingredients two general types of solid propellants can be distinguished. These are homogeneous (double-
base) and heterogeneous (composite) solid rocket propellants. The homogeneous propellants have a uniform
physical structure of chemically bonded fuel and oxidizer ingredients forming a single chemical structure whereas in
heterogeneous ones, the oxidizer and fuel are physically mixed but do not have chemical bonds between them.
Typical double base rocket propellants, consist mainly of nitrocellulose 50-60% and nitroglycerine 30-49% which
deliver energy to the system and other plasticizers, stabilizers, burning rate catalyst. Heterogeneous solid rocket
propellants are mixture of a solid oxidizer (ammonium perchlorate - AP) and liquid combustible substances
(binders) mostly synthetic rubber with functional groups, a cross-linking agent and various kinds of plasticizers and
additives. Modern solid rocket propellants have a number of properties desirable for efficient and safe operation.
The most important are: high chemical durability, good mechanical properties, high heat of combustion, low
sensitivity to ignition and detonation, low coefficient of thermal expansion, low molecular weight of combustion
products. Good repeatability of their thermal and mechanical properties is also essential for their safe handling and
production. [1].
Due to the nature of solid rocket propellants it is important to know their thermal and mechanical properties
which may affect the proper operation of the rocket motors [2, 3]. The glass transition (Tg) is considered a major
phase transition in polymers resulting in significant change in physical and mechanical properties of the material as
it goes from rigid glassy to rubbery state. For materials for which stiffness and strength are the most important
functional characteristics, the glass transition temperature means the upper limits of their applicability. For solid
rocket propellants, the glass transition area is the lower limit of their use. It is particularly important in case of their
resistance to dynamic loads during ignition and rocket take-off at very low temperatures [4]. The change of
mechanical properties due to phase transition in the material can result in the formation of cracks and voids leading
to an uncontrolled increase in burning surface of the propellant causing malfunction of the rocket motor or, in the
worst case explosion [3]. The glass transition temperature is affected by chemical composition and in case of solid
rocket propellants by the amount of plasticizers. In the DB rocket propellants, nitrocellulose is plasticized by
nitroglycerin, therefore the concentration of nitroglycerin and NC/NG ratio has a significant influence on the
mechanical properties as well as on the transition temperatures [5, 6].

EXPERIMENTAL PROCEDURE

Materials

Two types of solid rocket propellants, homogeneous PAC and heterogeneous H2 were tested to determine the
glass transition temperature. The basic chemical content of the two tested propellants is presented in Table 1.

TABLE 1. Tested propellants

PAC,  = 1.51 g/cm3 H2,  = 1.77 g/cm3
Ingridient Content % Ingridient Content %
Nitrocellulose 47.7 Amonium perchlorate 70
Nitroglycerin 28.4 Aluminium powder 15
Dinitrotoluen 7.3
Polyoxymethylene 7.3 BKN, additives, stabilizers ect. 15
Other additives 9.3

Methods

The experimental part of the work involved the use of three thermal analysis techniques. Differential scanning
calorimetry was applied for determining the glass transition temperature on the basis of the specific heat change
during heating. For testing of the two selected propellants the flow type differential microcalorimeter NETZSCH
DSC 404 F1 Pegasus device was used with the heating rate of 10 K/min in the temperature range from -100 oC to
100 oC. Determination of the specific heat required by the DSC technique, as accurately as possible, requires the
generation of three measurement curves: for empty sample crucibles, for the tested sample and for reference material
with constant heating / cooling speed and the same temperature program in each run. [7, 8]. For the measurements of
thermal expansion the NETZSCH DIL 402 SU was used. The test were carried out in the temperature range from
-100 oC to 110 oC with the heating rates of 2 and 10 K/min. A relatively high heating rate of 10 K/min in DIL
experiment was chosen so as to increase method sensitivity while searching glass transition region in the tested solid
rocket propellants. Dynamic mechanical analysis conducted in dual cantilever bending mode using the NETZSCH
DMA 242C analyzer over temperature range from -110 oC to +120 oC, with the heating rate of 2 K/min and the
frequency of 1 Hz. The glass transition was determined for both propellants from the peak of loss modulus curve. To
achieve sub-zero temperatures liquid nitrogen was used in all experiments.

RESULTS AND DISCUSSION

The DSC tests were performed for solid homogeneous PAC rocket and heterogeneous H2 propellants.
Using the DSC technique, the glass transition temperature Tg of the tested rocket propellants was determined from
the temperature dependence of specific heat presented in Figure 1. The selection of the temperature range in which a
glass transition occurs is optional, and therefore errors are possible with the determination of the boundaries of this
range. The glass transition value determined from the cp curve is taken as the middle value of the range marked in
Figure 1. In the same figure, the position of the cp peak corresponding to the temperature of 104.8 oC is marked,
which is associated with the unfinished endothermic transformation.

FIGURE 1. DSC experiment for PAC propellant.

Table 2 summarizes the DSC results of the glass transition temperature of the analyzed solid rocket
propellants. For homogeneous propellant PAC, the glass transition temperature (mid) is -38.8 °C, while for
heterogeneous propellant H2 is equal to -25.8 oC. The change in the specific heat value occurring with the transition
has the value of 0.107 Jg-1K-1 for PAC and 0.006 Jg-1K-1 for H2 propellant. It would therefore be impossible to
determine the glass transition temperature for the H2 propellant, from the cp curve without knowing the indicative
area of search.

TABLE 2. The glass transition temperature of the tested propellants determined from the cp curve
Glass transition temperature
Propellant
Onset [0C] Mid [0C] Inflection [0C] End [0C] Cp* [J∙g-1∙K-1]
PAC -51.2 -38.8 -44.6 -26.5 0.107
H2 -29.4 -25.8 -25.5 -21.6 0.006

Dilatometer experiments provided results of relative elongation (dL/Lo) and differential coefficient of
thermal expansion (diff CTE) dependence on temperature. The experiments were conducted in two courses with two
different heating rates. Previous experiments of solid rocket propellants [9] provided knowledge of the temperature
range of finding the onset of the dL/Lo curve, which is believed to correspond with the glass transition temperature.
Figures 2 and 3 present the results of thermal expansion tests for homogeneous PAC and heterogeneous H2 solid
rocket propellants respectively.
 FIGURE 2. DIL experiment for PAC homogeneous propellant.

FIGURE 3. DIL experiment for H2 heterogeneous propellant.

The average temperatures of the onset of the relative elongation curves for the two heating rates equal
-35 oC for PAC propellant and -53 oC for and H2 propellant. These temperature values are close to previously
researched with other thermal analysis techniques for both types of propellants. Nevertheless the onset of the dL/Lo
curve for both propellants is difficult to distinguish regardless of the heating rates applied.
The third experimental technique used was dynamic mechanical analysis (DMA). In contrast to the other two
applied methods the DMA allows to determine the temperature characteristics of the mechanical properties of the
tested material instead of thermal properties. As it was mentioned previously the glass transition results in
significant change of physical and mechanical properties of the material, therefore DMA is the most suitable method
for testing of solid rocket propellants. Figure 4 and 5 present temperature dependence of dynamic storage modulus
(E’), dynamic loss modulus (E”) and tangent of the phase angle (tan) for PAC and H2 solid rocket propellants
respectively. The glass transition region for solid rocket propellants, determined with the DMA technique occurs
between the onset of the E’ curve and the peak of the tan curve in the temperature range below 0 oC. Following the
recommendation of the NATO STANAG 4540 standardization agreement, for comparison purposes, the glass
transition temperature can be read from the clearly distinctive peak of the loss modulus curve [10].
 FIGURE 4. DMA experiment for PAC homogeneous propellant.

FIGURE 5. DMA experiment for H2 heterogeneous propellant.

The glass transition temperature determined from the peak of the E” curve equals -39.1 oC for PAC
homogeneous propellant and -56.5 oC for H2 heterogeneous propellant. The second peak of the tan is related with
the softening temperature of the material. This value along with the glass transition temperature sets the temperature
limit of safe operation of solid rocket propellants. The results of glass transition temperature of all applied thermal
analysis techniques are summarized in Table 3. It is worth mentioning that the most reliable result is the value
determined with the use of dynamic mechanical analysis while the results from dilatometry and differential scanning
calorimetry may be burdened with some level of uncertainty resulting from optional selection of the temperature
range. Compering the results confirms the low reliability of DSC result in case of heterogeneous H2 propellant.

TABLE 3. Glass transition temperature results

Analytical technique
Propellant
DSC DIL DMA
PAC -38.8 oC -35 oC -39.1 oC
H2 -25.8 oC -53 oC -56.5 oC
 CONCLUSIONS

Thermal analysis of solid rocket propellants was conducted with special attention given to the
determination of the glass transition temperature, a key factor for safe usage of solid rocket propellants under
operating conditions. The experiments involved the use of differential scanning calorimetry, dilatometry and
dynamic mechanical analysis of homogeneous propellant PAC and heterogeneous propellant H2. On the basis of
experiments, the following conclusions can be drawn:

1. The glass transition temperature determined with the use of DSC or DIL analysis can be misleading as the
selection of the temperature range of occurring transition is optional. Reliable result can still be obtained
with these methods, but it requires knowledge about the thermal properties of selected type of propellant or
results from other, more sensitive experimental techniques.
2. As the glass transition is related with significant change of mechanical properties of materials rather than
thermal properties it should be determined with a suitably sensitive technique. Dynamic mechanical
analysis proved to be an accurate and reliable method for testing solid rocket propellants and setting the
temperature limit of their safe operation. In accordance with the recommendations in the STANAG 4540
standardization agreement the glass transition temperature in solid rocket propellants can be directly and
easily distinguished from the peak of the loss modulus curve.
3. At the same time the limits of the glass transition region set between the onset of the E’ curve and the peak
of the tan curve can be the basis of glass transition temperature determination by DSC or DIL methods.
4. Despite the lack of reliability of determining the glass transition temperature with the use of dilatometry,
thermal expansion of solid rocket propellants in sub-zero temperature range is an important property in
terms of efficient and safe use of rocket motors. Further research in this field will be continued.

REFERENCES
1. K.K. Kuo, R. Acharya, Applications of turbulent and multiphase combustions, Solid propellants and their
combustion characteristics, 4-15,Wiley, 2012.
2. P. Folly, P. Mäder, Propellant Chemistry, Chimia 58, pp. 374-382, 2004.
3. G. Herder, F.P. Weterings, W.P.C. Klerk, Mechanical analysis on rocket propellants, Journal of Thermal
Analysis and Calorimetry, 72, pp. 921-929, 2003.
4. M. Miszczak, J. Borkowski, H. Terenowski, An analysis of test methods on physicochemical properties of
solid rocket propellants on the basis of the Polish standards, Issues of Armament Technology, 110,
pp. 133-141, 2009.
5. PN-EN-ISO 6721-1, Determination of dynamic mechanical properties - part 1 general principles, 2011.
6. J. Tucker A Whole Life Assessment of Extruded Double Base Rocket Propellants, PhD Thesis, Department
of Engineering and Applied Science, 2012.
7. M. Szumera, Charakterystyka wybranych metod termicznych (cz.1), LAB, 17, 6.
8. B. Wunderlich, Thermal Analysis of Polym. Mat., Springer-Verlag, Berlin Heidelberg 2005.
9. M. Cegła, J. Zmywaczyk, P. Koniorczyk, Thermo-mechanical analysis of homo- and heterogeneous solid
rocket propellants. Advanced Material Research Vol.1126 (2015), 194-200.
10. NATO Standardization agreement 4540, Explosives, procedures for dynamic mechanical analysis (DMA)
and determination of glass transition temperature, Edition 1, 2002.

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